acetylene



ame '12, 1940 2,192,931

John Groves Paton and Edmond George Williams, Northwich, England, assignors to Imperial Chemical Industries Limited, a corporation of 1 Great Britain No Drawing. Application October 22,1937, Serial 1 170,445., In Great Britain October 28,

4 Claims. ((1260-92) This invention relates to new compositions of sure conditions employed. Since the oxygen presmatter andmore particularly to valuable polyent in theethylene appears to be consumed durmerised products ing this rapid or kick reaction, it is necessary This invention has as an object the manufacto add more oxygen to the ethylene if a further ture of new and useful polymerised hydrocarbons. rapid polymerization is to be effected. If this 5' A further object is the production of polymerised is not desired, however, the polymerization may products from mixtures of ethylene and acetylbe allowed to continue slowly after the initial ene which have unusual and valuable prope reaction If the ygen content of the Stillother objects reside in methods for making ethylene is very low the requirement for the In our new polymeric material. Other objects will rapid removal of the heat of reaction is less-imappear hereinafter, portant than when (within the allowable range) These objects are accomplished by subjecting a the oxygen content is relatively high buhthe mixture of ethylene and acetylene to high presyield of polymer is lower i th former t in I sureat elevated temperature as will more fully the latter case. Generally, however, the more appear in the following description. eilicient the removal of the heat of reaction the By highpressure is meant a pressure of 500 higher the tolerable oxygen content of the ethatmospheres or more. Since the temperatures, ylene. pressures, and operating conditions generally Now we have found that if, instead of ethylene usedin the manufacture of our new polymerised as in the above mentioned processes, a mixture of products substantially follow the methods deethylene and acetylene is subjected to the condi- 20 scribed for making the new solid and semi-solid tions of high temperature and pressure described polymers from ethylene in Patent 2,153,553, and above, with or without the use of small amounts in application Serial Number 157,810 filed August of added oxygen, polymerisation products of high 6, 1937, by us jointly with M. W. Perrin, reference molecular weight are obtained which differ markmay be advantageously made to the processes edly from the ethylene polymers of the above 5 described in said applications for a complete unmentioned applications.

derstanding of the present invention. The following example is illustrative of the The, reaction conditions for producing the methods used in practicing our invention: above mentioned ethylene polymers comprise the E use of. pressures of at least 500 atmospheres and f preferably at least 1000 atmospheres; the use of Amixture comprising ethylene with about 20% moderately elevated temperatures between about of acetylene, also containing a small amount, 100 and about 400 0., and preferably between about 0.05%, of oxygen, is compressed to 1500 atabout 150 and about 250 C.; careful control of mospheres, then heated to 230 C. for 12 hours. 3 the thermal conditions during the polymeriza- About 25% ,byweight of the initial mixture is 85 tion, in the sense that the heat of reaction must converted into a yellow oil of remarkably ood i be rapidly dissipated to avoid an undue rise in drying properties, thus, when dissolved in a volatemperature. In the absence of oxygen the retile solvent and spread on a surface, a film is action is a relatively slow one proceeding smoothformed (after removal of the solvent) which dries 40 ly over a number of hours, at the end of which to a tack-free condition in about 1 hour. The 40 time a large proportion (up to 90%) of the ethyl-. drying time can be reduced still further, e. g. to ene has been converted. about 30 minutes, by the incorporation of a suit- However, if in accordance with the procedure able drying catalyst, e. g. cobalt oleate. described. .in said application Serial Number At somewhat higher temperatures, e. g. 270- 157,810 small but definite amounts of oxygen, us- 280C 9. higher yield of a similar yellow oil is 45 ually from 0.01% to 5%, are included with the obtained.

ethylene, the reaction is very rapid,lmanifesting Whenthe proportion of acetylene is small, the itself by a sudden pressure rise on the gauge, folproduct is a solid, but with increasing proportions lowed by a slow pressure drop. 'During this rapid of acetylene in the initial mixture, the molecular reaction from about 5% to about 20% of the ethweight of the product, for a given set of operatylene is polymerized, the particular yield of polying conditions, falls and the product'is more liqmer being dependent upon the oxygen content of uid. With substantial proportions of acetylene, the ethylene. The amount of oxygenrequired to such as about 15% or more, the product is, as in initiate this rapid polymerization reaction is genthe above example, an oil characterized by rer erally dependent upon the temperature and presmarkable drying properties. 1

Unlike the reaction with ethylene alone, there is apparently no kick or very rapid reaction with oxygen-containing mixtures of ethylene and acetylene, although-the presence of oxygen appears to favour the conversion. With mixtures of 20 per cent acetylene and 80 per cent ethylene, we have used up to 0.25 per cent of oxygen up to 240 C., without explosion if the mixture is adequately stirred.

10 Our new products are also compatible with other drying oils such as linseed oil stand oil and may be mixed with such drying oils to accelerate their drying.

As many apparently widely diflerent embodi- 1 ments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

30 We claim:

1. A process for producing polymers which comprises subjecting a mixture of ethylene and acetylene which contains at least 15% acetylene to a pressure above about'500 atmospheres and a temperature above about 100 C.

2. A process for producing polymers which comprises subjecting a mixture 01' ethylene and acetylene which contains at least 715%. acetylene and which contains a small amount of oxy en to a pressureabove about 500 atmospheres and a temperature above about 100 C.

3. A process for producing polymers which .comprises subjecting a mixture of ethylene and 

